Fatty derivatives of alkylated amines



Patented May 14, 1940 UNITED STATES FATTY DERIVATIVES F ALKYLATED AMINES Jacob Katz, Providence, R. I., assignor to Warwick Chemical Company, West Warwick, R. I., a corporation of Rhode Island No Drawing.

Application March 1, 1938,

Serial No. 193,262

4 Claims.

The present invention relates to the manufac ture of fatty derivatives .of alkylated amines and particularly relates tothe manufacture of fatty acid amides which are valuable as assistants in 5 the textile, leather and allied industries.

The invention further relates to an improved finishing process for textiles wherein novel effects are produced giving the textile an improved hand and enhanced texture, said improved finishing being accomplished by the use of alkylated amine derivatives.

The usual type of assistants or emulsifying agents which are utilized in the textile, leather, paper and allied industries are of the nature of l soaps or suiphonated compounds having high molecular weight fatty acid groups which are combined with alkali metals, the usual compounds being the sodiumsalts of the fatty acids or the sodium salts of sulphonated or sulphated fatty 20 acids, alcohols or ketones.

These compounds in the presence of water or in water solution tend to split into positively charged sodium ions and negatively charged high molecular weight fatty ions.

in baths containing substantial concentrations of heavy metal or alkaline earth metal ions since the fatty materials tend to combine with the heavy metals and alkaline earth metals to form insolu- 30 ble materials which are precipitated.

Moreover, the presence of substantial amounts of acid in the bath tend to split out the fatty matter and cause precipitation of the fatty material.

It is among the objects of the present invention 35 to produce new chemical compounds having the It is further desired to produce compounds of the character above described which, when applied to fabrics or other textiles, or other materials, for softening or for conditioning purposes will remain substantially-permanent upon such fabrics even though said fabrics be worn or vigorously washed many times and it is among As a result, these materials are of little value.

the further objects of the present invention to produce compounds of this character and method of treating fabrics. which will produce these results.

condensed with fatty acids or high molecular 10 weight saturated or unsaturated aliphatic acid compounds to produce amido compounds of unusual properties and of great value.

It has been found most satisfactory'to utilize an aliphatic amine preferably containing from two to twenty carbon atoms, which may contain two or more amino groups, which in the preferred embodiment are attached to different carbon atoms. These amines are included in the claims by the expression low molecular weight aliphatic polyamine.

Although these amino groups may be substituted by methyl, ethyl, propyl or other alkyl or aryl or aralkyl groups, it has been found most satisfactory to employ primary amino groups.

In respect to the fatty acids, they may contain from eight to thirty carbon atoms and preferably from ten to twenty carbon atoms and if desired, they may contain one or more unsaturated bonds or one or more hydroxy groups. These fatty acids are included in the specification by the expression high molecular weight fatty acid.

The carboxy group is preferably at the end of the carboxy chain although in certain instances it may be positioned at intermediate portions of the aliphatic chain.

In certain cases, sulpho, hero, or phospho grou may be attached to the aliphatic chain at the en s or intermediate portions thereof which groups may be amidized at the same time as the carboxy groups.

In some instances, the boro-phosphoor sulpho groups themselves may be amidized and the carboxy groups may be omitted or eliminated or they may be converted intoester groups or even into alcohol, ketone or aldehyde groups, by esterification or reduction processes.

It is an important feature of the present invention that there are utilized at least two mols of a fatty acid for every moi of a poly-amino 60 non-hydroxy aliphatic compound having two or more primary amino groups. l

Among the amines which may be employed are ethylene diamine, dicthylene tramine, triethylene tetramine, glycine amide. and various di. tri,

tetra and poly amines of normal, iso or tertiary propanes, butanes, pentanes, hexanes, cyclanes or unsaturated olefines, having from two to eight carbon atoms.

These aliphatic compounds may in some instances contain ether, keto, nitro, carboxyl or sulpho groupings.

The preferred fatty acids are lauric, myristic, palmitic, ricinoleic, oleic, stearic, eleostearic, hydrogenated abietic, cyclo carboxylic or other acids in which the chains or rings are homogeneous or heterogeneous containing from two to twenty-four carbon atoms and one or more carboxy groups and are also in some instances containing as elements of the chain or ring -CH2, -O-, -S, CO, N and other groupings.

The preferred compounds, however, are those formed from ethylene diamine, triethylene tetraamine and the fatty acids, lauric, myristic, palmitic, oleic and stearic.

The condensation reaction between the two or more mols of the acid-and the one mol of the polyamine may be conducted at atmospheric or reduced pressures, reduced pressures producing lighter colored products.

The temperature reaction may range between 50 and 200 C. and sometimes up to 250 C. and

the temperatures are gradually increased as the strong bases or acids because of their amphoteric properties.

Among the acids which may be employed for solubilizing the final amides are acetic, formic, lactic, propionic, boric, sulphonic acids, alkyl phosphoric acids, and so forth.

The amide being insoluble and not readily emulsiflable, may be deposited upon textile fibers or fabrics, whether woven or knitted, by modification, elimination orremoval of the solubilizing agent, with assurance that it will remain in position and give an unusual and distinct feel to the fabrics.

For example, acetic or formic acids may be readily volatilized away leaving the amide upon the fabric. This deposition may be carried put after the fabrics have been impregnated or sprayed with the solution of the amide and the amides may be or consist of other amides than those specifically disclosed, such as compounds of the type R-aCONXz where Rajs an alkyl having from eight to thirtycarbon atoms, and X is hydrogen, or an aliphatic or aromatic grouping.

inasmuch as they will not precipitate in the presence of acids, or heavy metal or calcium salts.

In forming the final compounds, there is first an interaction of an alkyl polyamine containing .at least two amino (NHz) groups. with as many 7 mols of fatty acid as there arenmino groups.

This reaction is as follows:

iii. R: and represent the same or different alkyl groups. Ra preferably .being higher and R1 and R2 lower alkyl groups.

The compounds are particularly satisfactory of amides by heating the above addition product until the calculated quantity of water is split out of the molecule.

This reaction is approximately as follows:

(2) RlC O OHJNHIRINHRQNHLHO O C R11 Example I 568 parts (2 mols) of stearic acid are melted in a 2 liter Calissen distilling flask (the side arm equipped with a water cooled condenser) and raised to a temperature of C. whereupon 103 parts (1 mol) of diethylene triamine are slowly added. The reaction is strongly exothermic and the heat of reaction raises the temperature to to C. The product which at first had turned to a yellow-orange jelly becomes liquid and heating is again resumed. When the mass has been raised to 160 C., the product suddenly begins to froth and foam and the second amide-forming reaction takes place. Heat is continually applied, the temperature remaining practically constant while the water of reaction is collected in the drip. When the frothing subsides the reaction is over and the temperature begins to rise.

The drip contains 36 grams (2 mols) of water (as calculated) together with a small quantity of the alkyl amine. The resulting product is a light yellowwaxy solid-melting point about 100 to 105 C. (depending on the heat treatment) and insoluble in water.

Example II One mol of cocoanut oil fatty acid and one mol of Japan wax fatty acid are reacted as above,-

tive in Example I, and lacks the hard waxy ap-.

pearance. It is insolublein water.

Example III One mol of lauric acid and one mol of chlorinated stearic acid are reacted with one mol of triethylene tetramine by slowly adding the tetramine to the molten fatty acids at a reduced pressure of 100 mm. The mixture is slowly heated at C. when the frothin'g begins. The calculated amount of water is collected in the drip and the reaction is stopped. The product is a hard yellow waxy substance insoluble in water.

It is, of course, possible to utilize other mixtures of acids than those above described, such as mixtures of oleic and palmitic acid or lauric and myristic acids, and in some cases the oils, fats or waxes themselves may be employedwhere the glycerine or basic part of the molecule will be split off and may be removed by distillation under vacuum or by steam, or in some cases, the split product may be left in the reaction mixture.

.It is also possible to condense the amines and the fatty acids with aromatic or other compounds during the condensation reaction and this may be accomplished by adding small quantities of condensing agents such as aluminum chloride, chloro-sulphonic acids, and so forth.

'- The preferred condensation materials are aromatic compounds, such as cresols, xylenols, benzene toluene, naphthalene and other unsubstituted or substituted monoor poly-nuclear hydrocarbons. I

The final products produced which may be sulphonated, phosphated and /01' borated are most valuable agents for wetting and dispersing purposes and may be most satisfactorily employed in ,fulling baths, dye baths, bleaching baths and mercerizing baths.

The compounds may be utilized by themselves or in combination with other agents for the treatment of yarns or woven or knitted textiles of silk, rayon, cotton, cellulose, acetate, or wool in the treatment of leather, paper and wood, in the manufacture of ceramics, in the metal and electro-plating industries, and for many other purposes. The amides can stand high concentration of heavy metals and strong acids, such as used in pickling and electro-plating baths.

A particular valuable application of the above identified compound resides in its application to yarns or woven and knitted fabrics to give them an improved soft hand and suede-like finish which may be attained with as little as 0.05 to 0.2% of the above amido compounds.

The above mentioned and other ingredients included in the invention may be added in various combinations and proportions to produce a final product of the desired physical and chemical properties. Hence, the application is not limited to the particular chemicals, quantities, temperatures, or steps of procedure specifically mentioned, as those are given simply as a means of clearly describing the invention.

It has not been most satisfactory to use condensation products of pclyamines and fatty acids having a proportion of less than-two mols of the fatty acid to one of the amine, as these compounds do not give the desirable hand or suede-like finish and also in certain instances, tend to have a stripping action.

Where the preferred compounds of the present invention are solubilized or given wetting or emulsifying properties they are solubilized or concerted by treatment with acids or acidic materials.

The present specification and claims are directed specifically to the use of the preferred novel compounds of the present application, while pounds of the present application per se.

a divisional application filed February 12, 1940, Serial No. 318,591 is directed to the novel compreferred materials are generally cation active. It is to be understood that the invention is not intended to be restricted to any particular example, composition or proportions, or to any particular application, or to any specific manner of use or to any of various details thereof, herein described, as the same may be modified in various particulars to be applied in many varied relations The.

without departing .from the spirit and scope of the claimed invention, the practical embodiments herein described merely showing some of the various features entering into the invention. I

What is claimed is:

1. A process of giving yarns and woven and knitted fabrics an improved soft hand and a suede-like finish which comprises treating such fabrics with an aqueous bath containing between 0.05%and 2.0% of a combination of one mol of the application of low molecular weight aliphatic polyamine and at least two mols of a high molecular weight, fatty acid.

2. A process of giving yarns and woven and knitted fabrics an improved soft hand and a suede-like finish which comprises treating such fabrics with an aqueous bath containing between 0.05% and 2.0% of a combination of two mols of stearic acid and one mol of diethylene triamine.

3. A process of giving yarns and woven and knitted fabrics an improved soft hand and a suede-like finish which comprises treating such fabrics with an aqueous-bath containing between 0.05% and 2.0% of a combination of one mole of low molecular weight non-hydroxy aliphatic polyamine and at least two mols of a high molecular weight fatty acid solubilized by a small amount of weak water soluble acid.

4. Textile yarns and fabrics having a not readily emulsiflable deposited surfacing of a combination of one mol of a low molecular weight aliphatic polyamine and at least two mols of a high molecular weight fatty acid, said, coating giving to said yarns and fabrics a. soft hand and a suede-like finish.

a v JACOB KATZ. 

